WO2011006780A1 - Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse - Google Patents
Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse Download PDFInfo
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- WO2011006780A1 WO2011006780A1 PCT/EP2010/059465 EP2010059465W WO2011006780A1 WO 2011006780 A1 WO2011006780 A1 WO 2011006780A1 EP 2010059465 W EP2010059465 W EP 2010059465W WO 2011006780 A1 WO2011006780 A1 WO 2011006780A1
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- composition
- cerium
- cerium oxide
- composition according
- oxide
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- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 41
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title description 11
- 238000002360 preparation method Methods 0.000 title description 8
- 239000011148 porous material Substances 0.000 claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 34
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims description 23
- 229910052684 Cerium Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- -1 sulphate ions Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 150000003755 zirconium compounds Chemical class 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002609 medium Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 229940044927 ceric oxide Drugs 0.000 description 3
- 150000001785 cerium compounds Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011872 intimate mixture Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003114 praseodymium compounds Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
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- C01B13/363—Mixtures of oxides or hydroxides by precipitation
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- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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Definitions
- the present invention relates to a composition based on cerium oxide and zirconium oxide of specific porosity, its method of preparation and its use in catalysis.
- multifunctional catalysts are used for the treatment of the exhaust gases of internal combustion engines (automotive post-combustion catalysis).
- Multifunctional means catalysts capable of operating not only the oxidation in particular of carbon monoxide and hydrocarbons present in the exhaust gas but also the reduction in particular nitrogen oxides also present in these gases (catalysts "three ways").
- Zirconium oxide and ceria appear today as two particularly important and interesting components for this type of catalyst.
- Products of this type must have a porosity adapted to their use. Thus, they must have pores large enough to allow good diffusion of gases.
- the object of the invention is to propose a product that achieves this compromise.
- the composition according to the invention is based on cerium oxide and zirconium oxide in a proportion of cerium oxide of at least 30% by weight, and it is characterized in that it has after calcination at a temperature of 900 ° C.
- two pore populations whose respective diameters are centered for the first, around a value of between 5 nm and 15 nm for a composition whose cerium oxide content is between 30% and 65% or a value between 10 nm and 20 nm for a composition whose cerium oxide content is greater than 65% and, for the second, around a value between 45 nm and 65 nm for a composition whose cerium oxide content is between 30% and 65% or a value between 60 nm and 100 nm for a composition whose cerium oxide content is greater than 65%.
- compositions of the invention have a significant population of small pores which contributes to give a high specific surface even at high temperature.
- compositions of the invention are in the form of particles which can be easily deagglomerated and which can lead to particles of much smaller size, which makes these compositions particularly interesting in catalysis applications.
- FIG. 1 is a porogram of a composition according to the invention after calcination at 900 0 C;
- FIG. 2 is a porogram of a composition according to the invention after calcination at 1000 ° C.
- rare earth is understood to mean the elements of the group consisting of yttrium and the elements of the Periodic Table with an atomic number inclusive of between 57 and 71.
- specific surface is meant the specific surface B. AND. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Chemical Society, 60, 309 (1938)".
- the calcinations at which the surface values are given are calcinations under air.
- the contents are given in oxide mass unless otherwise indicated in relation to the total mass of the composition.
- the cerium oxide is in the form of ceric oxide, the oxides of the other rare earths in the form Ln 2 ⁇ 3, Ln denoting the rare earth, with the exception of praseodymium expressed in the form Pr 6 On.
- the particle size values are obtained by measurements using the laser diffraction technique and carried out with a Coulter type apparatus.
- compositions of the invention are in two embodiments which differ in the nature of their constituents.
- these compositions are based on cerium oxide and zirconium oxide. More specifically, they may be compositions which consist of, or consist essentially of, cerium oxide and zirconium oxide. By this is meant that the composition contains no other oxide of another element which may be a constituent element of this composition and / or a stabilizer of the surface thereof, such as for example a rare earth. On the other hand, the composition may contain the impurities usually present with cerium and zirconium.
- the compositions are based on cerium oxide, zirconium oxide and at least one oxide of a rare earth other than cerium. It is therefore in this case compositions which contain at least three oxides.
- the rare earth other than cerium may in particular be chosen from yttrium, lanthanum, neodymium and praseodymium.
- compositions according to this second embodiment those based on cerium oxide, zirconium oxide, lanthanum oxide and praseodymium oxide, based on cerium oxide, oxide of zirconium, lanthanum oxide and neodymium oxide, based on cerium oxide, zirconium oxide, lanthanum oxide and ytthium oxide.
- the invention is to be understood as applying to the case where the composition consists of, or consists essentially of, cerium oxide, zirconium oxide and at least one other oxide of another rare earth, the composition then not containing any oxide of an element other than the aforementioned three and which could be a constituent element of this composition and / or a stabilizer of the surface thereof.
- the composition may contain the impurities usually present with the zirconium and rare earth elements.
- compositions of the invention do not contain a noble metal or precious metal element as a constituent element.
- the term "constituent element” means, for this type of metal, that the metal in question could be present in the composition, in the form of an intimate mixture with the other elements cerium, zirconium and where appropriate, rare earth other than cerium, such an intimate mixture being obtained by example when the noble or precious metal is used during the preparation of the composition itself.
- cerium and zirconium content of the compositions of the invention may vary widely, with the proviso that the cerium oxide content is at least about 30%.
- this content is such that the Ce / Zr ratio expressed as mass of oxides of these elements is between 3/10 and 9/10, more particularly between 2.5 / 2 and 8/2.
- the oxide content of the rare earth other than cerium may be more particularly at most 20% by weight. This content may be more particularly at most 15% and even more particularly at most 10%. It is also usually at least
- the cerium oxide content may be more particularly at least 40%, especially in the case of the compositions according to the second embodiment, and even more particularly at least 50%.
- the main characteristic of the compositions of the invention is their porosity.
- compositions of the invention have two distinct pore populations which are centered around the values given above.
- the term "population of pores centered around a given value” means the presence in the curve (C) of a peak whose maximum is situated at this given value.
- compositions of the invention are the fact that they retain this double population of pores, and therefore the related advantages, even at high temperature, for example even at a temperature above 900 ° C.
- the compositions of the invention after calcination at a temperature of 1000 ° C. for 4 hours, always have two populations of pores of small size and larger.
- the pore diameters are centered around a value of between 8 and 20 nm and, for the second, the diameters are centered around a value of between 30 nm and 70 nm for the compositions whose cerium oxide is between 30% and 50% or between 70 nm and 80 nm for compositions whose cerium oxide content is greater than 50%.
- the second population of pores is a narrowed or monodisperse population because most of the pores of this population have a size that remains very close to the value around which is centered the corresponding peak.
- This characteristic can be measured by the ratio of the width I of the peak at its mid-height to the width L of the peak at its baseline.
- this I / L ratio measured on the porograms after calcination at 900 ° C. or 1000 ° C., is generally at least 30%, more particularly at least 40%.
- compositions of the invention also have a total pore volume which is high.
- the compositions after calcination at 900 ° C., 4 hours have a total pore volume of at least 0.6 ml Hg / g.
- This pore volume may be more particularly at least 0.7 ml Hg / g.
- a pore volume value of about 0.90 ml Hg / g can be attained.
- the compositions may have a total pore volume of at least 0.5 ml Hg / g, more preferably at least 0.65 ml Hg / g. At this same temperature, a pore volume value of about 0.70 ml Hg / g can be attained.
- the total pore volume mentioned here is that resulting from pores whose diameter is between 3 nm and 100 microns.
- Another interesting feature of the invention is that the small pores, that of the aforementioned first population, contribute to a relatively large proportion of the total pore volume. This proportion depends on the temperature at which the composition was calcined, it is higher for the compositions that have been calcined at lower temperatures and can vary generally between 5 and 20%.
- this proportion can be between 8 and 12% in the case of calcination at 900 ° C. for 4 hours.
- compositions of the invention induces a large surface area thereof.
- compositions of the invention may have, after calcination at 900 ° C., 4 hours, a specific surface area of at least 30 m 2 / g, more particularly at least 45 m 2 / g for the compositions according to the second embodiment. After calcination at this same temperature, surface values up to about 35 m 2 / g and up to about 55 m 2 / g can be obtained for the compositions according to the first and second embodiments respectively.
- the specific surface area may be at least 15 m 2 / g for the first embodiment and at least 30 m 2 / g for the compositions according to the second embodiment. After calcination at this same temperature of surface values up to about
- the specific surface of the compositions of the invention may be at least 5 m 2 / g for the first embodiment and at least 15 m 2 / g for the compositions according to the second embodiment after calcination on the same embodiment. duration but at 1100 0 C.
- compositions of the invention are their ease of being disaggregated.
- compositions of the invention are in fact generally at the end of their preparation in the form of particles whose average size (d 5 o) is usually between 7 microns and 20 microns.
- These particles are in fact agglomerates which are easily disaggregated into aggregates of considerably smaller average size, in particular of at most 3 ⁇ m, more particularly at most 2 ⁇ m, which consist of crystallites aggregated with each other.
- micronization means that we can go from agglomerates to aggregates by a treatment that does not require significant energy, unlike grinding type micronization or wet type, for example.
- This treatment can be, for example, deagglomeration by ultrasound or by suspension.
- washcoats intended to be deposited on the monoliths.
- compositions of the invention have good phasic purity. These compositions can thus be in the form of solid solutions up to high temperatures, that is to say even after calcination at 1100 ° C., in particular for the compositions according to the second embodiment.
- the phase corresponds to that of a zirconium oxide crystallized in the tetragonal system, whose mesh parameters can also be shifted and similarly reflecting the incorporation of cerium and, optionally, other element in the crystal lattice of zirconium oxide.
- This process comprises the following steps:
- a first liquid medium which comprises a zirconium compound, a cerium III compound, sulphate ions, an oxidizing agent and, if appropriate, a rare earth compound other than cerium; the preceding medium is brought into contact with a base, whereby a precipitate is formed;
- the precipitate resulting from the preceding step is resuspended in water and the medium thus formed is subjected to a heat treatment at a temperature of at least 90 ° C .;
- the precipitate is separated and calcined.
- the first step of the process consists in forming a liquid medium which is water, preferably, and in which there are, in the necessary quantities, compounds of the various elements which form part of the composition of the composition which is to be obtained. to prepare. It is therefore zirconium compounds, cerium and, in the case of the preparation of a composition according to the second embodiment, the rare earth or rare earths other than cerium.
- These compounds will preferably be soluble compounds. It can be in particular salts of these elements.
- the cerium compound is a compound in which this element is in Form III. More particularly, mention may be made of halides, in particular chloride and nitrate.
- zirconium it is possible to use zirconyl nitrate or zirconyl chloride, zirconium sulphate, more particularly a zirconium ortho sulphate or else a basic zirconium sulphate.
- the compounds may be chosen from nitrates, sulphates, acetates and chlorides.
- the starting liquid medium must also contain an oxidizing agent which may be, for example, hydrogen peroxide.
- the starting liquid medium should also contain sulfate ions. These sulphate ions must be present in an amount such that the atomic ratio sulphate ions / Zr is at least 0.5, preferably at least 2.
- sulphate ions may be provided for example by sulfuric acid. They may also be provided at least in part by the zirconium compound when it is a sulfate compound.
- the second step of the process consists in bringing the liquid medium prepared in the first step into contact with a base.
- Hydroxide products can be used as a base. Mention may be made of alkali or alkaline earth hydroxides. Secondary and tertiary amines can also be used or quaternary. However, amines and ammonia may be preferred in that they reduce the risk of pollution by alkaline or alkaline earth cations. We can also mention urea.
- the base can be used more particularly in the form of a solution.
- the placing in the presence between the first liquid medium and the base can be done by introducing the medium into the base, for example by introducing the medium into a reactor which contains the base at the bottom of the tank .
- the bringing together or the reaction between the first liquid medium and the base can be carried out at once, gradually or continuously, and it is preferably carried out with stirring. It is preferably conducted at a temperature of at least 45 ° C.
- reaction with the base leads to the formation of a precipitate.
- This precipitate is separated from the reaction medium in which it has been obtained by any known means, for example by filtration.
- the separated precipitate is washed with water in order to remove the sulphates still present in the precipitate.
- This washing can be done with water at room temperature or with hot water, for example at a temperature of at least 50 ° C.
- the next step of the process is the step of heat treatment of the precipitate in an aqueous medium.
- This heat treatment is carried out on a suspension obtained after the washed precipitate is put back into the water.
- the temperature at which the medium is heated is at least 90 ° C., more particularly at least 100 ° C. and even more particularly at least 150 ° C., and it may be between 150 ° C. and 200 ° C. .
- the heat treatment operation can be conducted by introducing the liquid medium into a closed chamber (autoclave type closed reactor). Under the conditions of the temperatures given above, and in an aqueous medium, it is thus possible to specify, by way of example, that the pressure in the closed reactor can vary between a value greater than 1 bar (10 5 Pa) and 165 bar. (1, 65. 10 7 Pa), preferably between 5 Bar (5 ⁇ 10 5 Pa) and 165 Bar (1, 65. 10 7 Pa).
- the heat treatment may be conducted either in air or in an atmosphere of inert gas, preferably nitrogen.
- the duration of the heat treatment can vary within wide limits, for example between 1 and 48 hours, preferably between 1 and 24 hours.
- the rise in temperature is carried out at a speed that is not critical, and it is thus possible to reach the reaction temperature set by heating the medium. for example between 30 minutes and 4 hours, these values being given entirely as an indication.
- the recovered precipitate is separated from the medium in which the heat treatment has taken place by any suitable means, for example by filtration, and is then calcined.
- This calcination makes it possible to develop the crystallinity of the product formed and it can also be adjusted and / or chosen as a function of the temperature of subsequent use reserved for the composition according to the invention, and this taking into account the fact that the specific surface of the product is even lower than the calcination temperature used is higher.
- Such calcination is generally carried out under air, but a calcination carried out for example under inert gas or under a controlled atmosphere (oxidizing or reducing) is obviously not excluded.
- the calcination temperature is generally limited to a range of values of between 500 and 900 ° C., more particularly between 600 ° C. and 800 ° C.
- the precipitate can be separated by atomization of the liquid medium in which the heat treatment took place.
- Spray drying is understood to mean spray drying of the mixture in a hot atmosphere (spray-drying).
- the atomization can be carried out using any sprayer known per se, for example by a spraying nozzle of the watering apple or other type. It is also possible to use so-called turbine atomizers.
- spraying techniques that can be implemented in the present process, reference may be made in particular to the basic work of MASTERS entitled "SPRAY-DRYING" (second edition, 1976, Editions George Godwin - London).
- the dried precipitate thus obtained is subjected to calcination under the conditions which have been given previously.
- compositions of the invention as described above or as obtained by the method described above are in the form of powders but they may optionally be shaped to be in the form of granules, balls, cylinders or nests. bee of variable dimensions.
- compositions of the invention can be used as catalysts or catalyst supports.
- the invention also relates to catalytic systems comprising the compositions of the invention.
- these compositions can thus be applied to any support usually used in the field of catalysis, ie in particular thermally inert supports.
- This support may be chosen from alumina, titanium oxide, cerium oxide, zirconium oxide, silica, spinels, zeolites, silicates, crystalline silicoaluminium phosphates, phosphates of crystalline aluminum.
- compositions can also be used in catalytic systems comprising a coating (wash coat) with catalytic properties and based on these compositions, on a substrate of the type for example metallic monolith or ceramic.
- the coating may also include a support of the type mentioned above. This coating is obtained by mixing the composition with the support so as to form a suspension which can then be deposited on the substrate.
- catalytic systems and more particularly the compositions of the invention can find very many applications. They are thus particularly well adapted to, and therefore usable in the catalysis of various reactions such as, for example, dehydration, hydrosulfuration, hydrodenitrification, desulphurization, hydrodesulphurization, dehydrohalogenation, reforming, reforming.
- the catalytic systems and the compositions of the invention may finally be used as NOx traps or to promote the reduction of NOx even in an oxidizing medium or as catalysts in a process for decomposing N 2 O, for example in a production unit of nitric acid or in a static unit.
- the compositions of the invention are used in combination with precious metals, they thus play the role of support for these metals.
- the nature of these metals and the techniques for incorporating them into the support compositions are well known to those skilled in the art.
- the metals may be platinum, rhodium, palladium or iridium, they may in particular be incorporated into the compositions by impregnation.
- the treatment of the exhaust gases of internal combustion engines (automotive post-combustion catalysis) is a particularly interesting application. Therefore, the invention also relates to a method for treating the exhaust gases of internal combustion engines, which is characterized in that a catalytic system as described above or a composition according to the invention is used as catalyst. invention and as previously described.
- the porosities are measured by the technique and according to the standard mentioned above and under the following more particular measurement conditions:
- the samples subjected to the measurement undergo a degassing of 10 hours at 100 ° C. in a ventilated oven at 100 ° C. They have a mass of about 300 mg.
- a powder penetrometer No. 14 having a cell of 3.28 cm 3 with a capillary of 0.413 cm 3 is used .
- This example relates to the preparation of a composition based on zirconium oxide and cerium oxide in the respective proportions by weight of oxide of 20% and 80%.
- the zirconium compound used is zirconium ortho sulphate, in solution, obtained by dissolving zirconium basic sulphate with sulfuric acid at room temperature and whose concentration is 253.5 g / l with a density of 1 , 478, the cerium compound is a cerium nitrate Ce (NO 3) 3, in solution, whose concentration is 496 g / l with a density of 1.716.
- a mixture of the above compounds is made in the appropriate amounts to obtain a final oxide of the intended composition; 140 ml of 35% H 2 O 2 are then added to this mixture.
- the solution obtained is diluted to a concentration of 100 g / l and then it is introduced dropwise into a basic stock (consisting of 1500 ml of NH 4 OH 5 mol / l) with continuous stirring. After semi-continuous precipitation by pouring into a second reactor stirred continuously, the precipitate obtained is filtered and washed twice consecutively with repulping.
- the concentration in the precipitation reactor is 100 g / l throughout the reaction.
- the precipitate obtained in the overflow reactor is resuspended in water at 100 g / l and then it is introduced into an autoclave for 1 hour at 200 ° C. with stirring. The precipitate is then calcined in air at 850 ° C. for two hours.
- Second pore population centered at 80 nm at
- This example relates to the preparation of a composition based on zirconium oxide, cerium oxide, lanthanum oxide and praseodymium oxide in the respective proportions by mass of oxides of 30%, 60%, 3% and 7%.
- the zirconium and cerium compounds used are the same as in Example 1.
- the lanthanum compound is a La (NOs) 3, in solution, with a concentration of 454 g / l and a density of 1.687 and the
- the praseodymium compound is in the form of Pr (NO 3) in solution at 500 g / l with a density of 1.732.
- a mixture of the above compounds is made in the appropriate amounts to obtain a final oxide of the intended composition, then 107 ml of H 2 O 2 (concentration 11.6 mol / l and density 1.132) are added to this mixture.
- the solution obtained is diluted to a concentration of 100 g / l and then introduced dropwise into a basic stock (consisting of 1500 ml of NH 4 OH 5 mol / l) with continuous stirring. After precipitation and stirring for 1 hour at 50 0 C the precipitate obtained is filtered and washed twice consecutively with repulpage.
- the precipitate obtained is resuspended in water at 100 g / l to be introduced into an autoclave for 1 hour at 200 0 C with stirring. The precipitate is then calcined under air at 850 ° C for two hours.
- Second pore population centered at 45 nm centered at 60 nm at 900 ° C 4 hours 1000 0 C 4 hours
- the composition After calcination at 1100 ° C. for 4 hours, the composition is in the form of a pure cubic fluorite crystallographic phase.
- Figure 1 is the porogram of the composition of Example 2 after calcination at 900 ° C., 4 hours. We can see a first peak, starting from the right of the porogram, centered at 10 nm and a second peak centered at 45 nm.
- Figure 2 is a porogram of the same composition but after calcination at 1000 ° C, 4 hours. We find the same peaks as on the previous porogram but with a shift of these to the left, the first centered at 15 nm and the second at 60 nm.
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Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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JP2012519967A JP5564109B2 (ja) | 2009-07-17 | 2010-07-02 | 特有の多孔度を有する酸化セリウムおよび酸化ジルコニウムを含む組成物、この調製方法および触媒作用におけるこの使用 |
CN201080032484.8A CN102574696B (zh) | 2009-07-17 | 2010-07-02 | 基于氧化铈和氧化锆具有特定孔隙率的组合物、其制备方法及其在催化中的用途 |
KR1020127001151A KR101431919B1 (ko) | 2009-07-17 | 2010-07-02 | 비다공도를 갖는, 산화세륨 및 산화지르코늄을 포함하는 조성물, 그의 제조 방법 및 촉매작용에서의 그의 용도 |
CA2766212A CA2766212C (fr) | 2009-07-17 | 2010-07-02 | Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse |
PL10726996T PL2454196T3 (pl) | 2009-07-17 | 2010-07-02 | Kompozycja wytwarzana na bazie tlenku ceru i tlenku cyrkonu o specyficznej porowatości, sposób wytwarzania i zastosowanie w katalizie |
EP10726996.1A EP2454196B1 (fr) | 2009-07-17 | 2010-07-02 | Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse |
RU2012105476/05A RU2509725C2 (ru) | 2009-07-17 | 2010-07-02 | Композиция на основе оксида церия и оксида циркония с особой пористостью, способ получения и применение в катализе |
US13/384,593 US10384954B2 (en) | 2009-07-17 | 2010-07-02 | Composition comprising cerium oxide and zirconium oxide having a specific porosity, preparation method thereof and use of same in catalysis |
ZA2012/00352A ZA201200352B (en) | 2009-07-17 | 2012-01-17 | Composition comprising cerium oxide and zirconium oxide having a specific porosity, preparation method threrof and use of same in catalysis |
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FR0903506A FR2948116B1 (fr) | 2009-07-17 | 2009-07-17 | Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse |
FR09/03506 | 2009-07-17 |
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US (1) | US10384954B2 (fr) |
EP (1) | EP2454196B1 (fr) |
JP (1) | JP5564109B2 (fr) |
KR (1) | KR101431919B1 (fr) |
CN (1) | CN102574696B (fr) |
CA (1) | CA2766212C (fr) |
FR (1) | FR2948116B1 (fr) |
PL (1) | PL2454196T3 (fr) |
RU (1) | RU2509725C2 (fr) |
WO (1) | WO2011006780A1 (fr) |
ZA (1) | ZA201200352B (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US8530372B2 (en) | 2009-07-22 | 2013-09-10 | Basf Corporation | Oxygen storage catalyst with decreased ceria reduction temperature |
AU2012244381A1 (en) * | 2012-05-29 | 2013-12-19 | Joint Stock Company Scientific Industrial Enterprise Neftehim | Method for isomerization of paraffin hydrocarbons c4-c7 |
WO2017187085A1 (fr) | 2016-04-26 | 2017-11-02 | Rhodia Operations | Oxyde mixte a base de cérium et de zirconium |
EP2454196B1 (fr) | 2009-07-17 | 2018-03-21 | Rhodia Opérations | Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse |
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JP2018143955A (ja) * | 2017-03-06 | 2018-09-20 | イビデン株式会社 | ハニカムフィルタ |
JP6781742B2 (ja) * | 2018-09-12 | 2020-11-04 | イビデン株式会社 | ハニカム構造体 |
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WO2024033516A1 (fr) * | 2022-08-12 | 2024-02-15 | Rhodia Operations | Oxyde mixte à base de cérium et de zirconium |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2454196B1 (fr) | 2009-07-17 | 2018-03-21 | Rhodia Opérations | Composition a base d'oxyde de cerium et d'oxyde de zirconium de porosite specifique, procede de preparation et utilisation en catalyse |
US8530372B2 (en) | 2009-07-22 | 2013-09-10 | Basf Corporation | Oxygen storage catalyst with decreased ceria reduction temperature |
AU2012244381A1 (en) * | 2012-05-29 | 2013-12-19 | Joint Stock Company Scientific Industrial Enterprise Neftehim | Method for isomerization of paraffin hydrocarbons c4-c7 |
WO2017187085A1 (fr) | 2016-04-26 | 2017-11-02 | Rhodia Operations | Oxyde mixte a base de cérium et de zirconium |
WO2020178185A1 (fr) | 2019-03-03 | 2020-09-10 | Rhodia Operations | Oxyde mixte présentant un volume poreux élevé |
Also Published As
Publication number | Publication date |
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CA2766212A1 (fr) | 2011-01-20 |
FR2948116A1 (fr) | 2011-01-21 |
US20120189517A1 (en) | 2012-07-26 |
RU2509725C2 (ru) | 2014-03-20 |
PL2454196T3 (pl) | 2018-09-28 |
CN102574696A (zh) | 2012-07-11 |
EP2454196B1 (fr) | 2018-03-21 |
JP5564109B2 (ja) | 2014-07-30 |
CN102574696B (zh) | 2014-07-23 |
EP2454196A1 (fr) | 2012-05-23 |
ZA201200352B (en) | 2012-12-27 |
KR101431919B1 (ko) | 2014-08-19 |
RU2012105476A (ru) | 2013-08-27 |
CA2766212C (fr) | 2018-06-05 |
KR20120029475A (ko) | 2012-03-26 |
JP2012533499A (ja) | 2012-12-27 |
FR2948116B1 (fr) | 2012-05-04 |
US10384954B2 (en) | 2019-08-20 |
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